JPH10291967A - Modifier of compound having Si-H bond in molecule, amino-modified silicone and surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modifier useful for production of a low-irritant modified silicone having antimicrobial activity and excellent sustainability of the activity, by using a specific quaternary ammonium compound. SOLUTION: This modifier for a compound having intramolecular Si-H bond(s) is a quaternary ammonium compound expressed by formula I (R and R' are each H or methyl; R<1> and R<2> are each a hydrocarbon or a hydrocarbon containing O; X is an anionic atom or anionic group) and having 2 reactive carbon-carbon double bonds. As the compound having intramolecular Si-H bonds, a compound expressed by formula II [R<3> is H, OH or a hydrocarbon (which may contain O and/or Si); (n) is 0, or an interger of >=1] is preferable. The 2nd objective new amino-modified silicone is obtained by reaction between the subject modifier as the compound of formula I and a compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing Si-H
The present invention relates to a compound modifier having a bond. The present invention also relates to an amino-modified silicone modified with the modifier.

[0002]

2. Description of the Related Art Polydimethylsiloxane has excellent properties such as heat resistance, weather resistance, low toxicity, spreadability, and low surface tension, and is used in various fields. Also, in response to market demands, organically modified silicones in which a part of the methyl group is substituted with another organic substituent have been actively developed. Polyether-modified silicone and carboxylic acid-modified silicone are used in the field of paints for the purpose of preventing yuzu skin and improving surface smoothness at the time of coating, and also have an effect of improving dispersibility of pigments and preventing discoloration. In addition, amino-modified silicone has an effect of improving flexibility of fibers, an effect of improving combability to hair, and an effect of protecting hair, and has been used as a fiber treatment agent and a hair cosmetic. It has also been used as a paint additive because it improves blocking resistance when added to paints.

For example, Japanese Patent Application Laid-Open No. 6-65379 discloses that a specific organic surfactant substituent is introduced into a polydimethylsiloxane-based compound to provide excellent surface activity, dispersibility,
An organic surfactant-modified organopolysiloxane having excellent emulsifying properties, antistatic properties and antifogging properties is disclosed. This polyorganosiloxane is used in the production of urethane foams, such as foaming agents, cosmetics, release agents, defoamers, fiber treatment agents, adhesives, antifogging agents, polishes, water repellents, paints, antistatic agents, etc. Is disclosed as being useful. Also, Japanese Patent Application Laid-Open No. 6-220198
Discloses a modified polyorganosiloxane similarly substituted with a specific organic substituent, and this polyorganosiloxane is useful as a surfactant, an emulsifier, an antistatic agent, a fiber treatment agent, and a hair cleaner. It is described. Further, JP-A-7-316334 discloses that a polyorganosiloxane similarly substituted with a specific organic substituent is used as a foaming agent component of a rigid polyurethane foam. Also, Japanese Patent Application Laid-Open No. 8-155
No. 287 discloses a reactive surfactant obtained by hydrolyzing and polycondensing a reaction product obtained by subjecting a specific compound having a propenyl group and a compound having a Si—H bond in a molecule to a hydrosilylation reaction. , Emulsions, paints, and coating agents. JP-A-7-2964 discloses that cation-modified polysiloxane polymers are useful as hair treatment agents such as shampoos and rinses.
Further, Japanese Patent Application Laid-Open No. 8-31776 discloses that
It is disclosed that an amino group-containing organopolysiloxane having a quaternary amino group is useful as a fiber treatment agent for imparting flexibility and slipperiness to fibers.

[0004]

However, these modified silicones have not yet been able to achieve the performance required to meet the market demands, particularly when used in the field of fiber treatment agents, hair treatment agents or paint additives. In particular, when used as a fiber treatment agent or hair treatment agent, there is little irritation to the skin,
There has been a demand for a polyorganosiloxane or a polyorganosiloxane modifier which has antibacterial properties, and has a long-lasting effect of improving flexibility, hair protection and resin blocking resistance.

[0005]

Means for Solving the Problems The present inventors diligently studied and found that a quaternary ammonium compound having two reactive carbon-carbon double bonds can be used as a modifier for a compound having a Si-H bond in the molecule. The present invention has been found to be useful as such and has been completed. That is, the present invention provides the following general formula (1)

Embedded image (Wherein, R and R ′ represent a hydrogen atom or a methyl group, R ¹ and R ² represent a hydrocarbon group or a hydrocarbon group containing an oxygen atom, and X represents an anionic atom or an anionic group. And a compound having a Si—H bond in the molecule. Further, the present invention is an amino-modified silicone modified with the modifier.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound represented by the general formula (1) which is a modifier of the present invention, R or R '
Represents a hydrogen atom or a methyl group. That is, the compound represented by the general formula (1) is a quaternary ammonium compound having two (meth) allyl groups.

R ¹ and R ² represent a hydrocarbon group or a hydrocarbon group containing an oxygen atom. As the hydrocarbon group, for example,
Examples include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl and undecyl. , Dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl,
2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl and the like can be mentioned.

Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

The aryl group includes, for example, phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octyl Phenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl,
Examples include phenylphenyl, styrenated phenyl, benzylphenyl, p-cumylphenyl, α-naphthyl and β-naphthyl groups.

Examples of the cycloalkyl group and cycloalkenyl group include, for example, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcyclohepenyl And a thenyl group.

Further, R ¹ and R ² may be a hydrocarbon group containing an oxygen atom. A particularly preferred group as the hydrocarbon group containing an oxygen atom is a group represented by (R ⁴ —O) _m —H.
R ⁴ represents a hydrocarbon group, and R ⁴ is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene, propylene, butylene, isobutylene, and styrene oxide residue, or a styrene oxide residue (phenylethylene group). (R ^4-
O) The _m part can be obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and the like, styrene oxide and the like. Further, the alkylene oxide or styrene oxide to be added may be used to form R ⁴
The alkylene oxide or styrene oxide to be added may be a homopolymer, two or more random copolymers, a block copolymer or a random / block copolymer. The addition method may be a known method. R
⁴ is preferably an ethylene group, and when R ⁴ is two or more, one is preferably an ethylene group.

X represents an anionic atom or an anionic group serving as a counter ion. Examples of the anionic atom or anionic group include a chlorine atom, a bromine atom, an iodine atom, a methyl sulfate group, an ethyl sulfate group, and the like.

The compound modified by the modifier of the present invention is a compound having a Si—H bond in the molecule. The compound having a Si—H bond in the molecule is not particularly limited, but a typical compound is a compound represented by the general formula (2).

In the general formula (2), R ³ independently represents the same or different hydrogen atom, hydroxyl group, hydrocarbon group or hydrocarbon group having an oxygen atom and / or a silicon atom. The hydrocarbon group is not particularly limited, and the above-described hydrocarbon groups can be exemplified. However, if the hydrocarbon group is too large, it is difficult to produce a polysiloxane,
Preferably methyl, ethyl, propyl, isopropyl,
1 carbon atoms such as butyl, isobutyl, pentyl, hexyl, etc.
6 to 6 alkyl groups or phenyl, toluyl, xylyl,
It is an aryl group such as ethylphenyl, and more preferably a methyl group and / or a phenyl group. R ³ may be a hydrocarbon group having an oxygen atom and / or a silicon atom such as a (poly) oxyalkylene group and a (poly) alkylsilyloxy group. The compound represented by the general formula (2) has 2n + 6 R ³ groups, at least one of which must be a hydrogen atom. N represents 0 or a number of 1 or more. n is preferably 1 to 5,000, more preferably 1 to 1,000.

The amino-modified silicone of the present invention obtained by reacting the modifier of the present invention with a compound having a Si—H bond in the molecule is a novel compound. The mode of using the modifier of the present invention, that is, the method for producing the amino-modified silicone of the present invention is not particularly limited, and may be based on a known hydrosilylation reaction, but the reaction may be performed in the presence of a catalyst. It is efficient. Examples of the catalyst include a peroxide catalyst, an azo compound catalyst, a platinum catalyst such as chloroplatinic acid, a rhodium catalyst, a cobalt catalyst, a palladium catalyst, a nickel catalyst, and a trialkylamine. Among them,
The most efficient catalysts are platinum based catalysts such as chloroplatinic acid.
The amount of the catalyst used is not particularly limited, but usually, Si
10 ^-2 to 10 based on 1 mol of the compound having a -H bond
^-10 mol, preferably 10 ^-3 to 10 ^-7 mol. The reaction is usually carried out under normal pressure under the conditions of the modifier of the present invention and Si—H
The reaction is carried out by mixing a compound having a bond and a necessary catalyst without a solvent or in a solvent. Solvents include alcohol solvents, ketone solvents, ether solvents, ester solvents,
Cellosolve solvents, hydrocarbon solvents and the like can be mentioned. The reaction temperature is preferably 0 to 200 ° C, more preferably 50 ° C.
To 150 ° C., and the reaction time is preferably 10 minutes to 20 minutes.
Time.

Further, a modifying agent comprising the compound represented by the general formula (1), a compound having a reactive carbon-carbon double bond in the molecule, and a Si compound in the molecule represented by the general formula (2)
Amino-modified silicone obtained by reacting a compound having a -H bond is also a novel compound. The compound having a reactive carbon-carbon double bond in the molecule is a compound containing an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyl group, a crotonyl group, a propenyl group and the like, for example, a (poly) oxyalkylene Mono (meth) allyl ether, (poly) oxyalkylene di (meth) allyl ether, (poly) oxyalkylene monoalkylmono (meth) allyl ether, (poly) oxyalkylenemonoarylmono (meth) allyl ether, (meth) Acrylate, (poly) oxyalkylene mono (meth) acrylate, (poly) oxyalkylene di (meth) acrylate, (poly) oxyalkylene monoalkyl mono (meth) acrylate, (poly) oxyalkylene monoaryl mono (meth) acrylate, (Meth) allyl glyci Alkylene oxide adduct or a sulfate of a reaction product of ether and alcohol or phenol, alkylene oxide adducts of alkylpropenylphenol or sulfate, and the like. The reaction method is not particularly limited, and may be in accordance with the above-described reaction method.

The amino-modified silicone of the present invention has a surface activity. Therefore, surfactants, defoamers, emulsifiers,
Cleaning agents, dispersants, release agents, fiber treatment agents, adhesives, anti-fog agents, polishes, water repellents, foam stabilizers such as urethane foams,
Paint additives, antistatic agents, lubricants, resin internal lubricants,
It can be used as a resin modifier. Also, since it has a quaternary ammonium group in the molecule, it is particularly useful as a fiber treatment agent, hair treatment agent or paint additive.

When the amino-modified silicone of the present invention is used as a fiber treating agent, it is preferable to use it by emulsifying or dispersing it in water or an organic solvent. Also, other ingredients,
For example, silane compounds, crosslinking agents, antistatic agents, preservatives, p
H adjusters, polysiloxanes, surfactants, solvents, emulsifiers and the like can be added. When used as a fiber treatment agent, the amount used is not particularly limited, but is preferably 0.
The content is preferably from 0.01 to 30% by weight, more preferably from 0.05 to 20% by weight, even more preferably from 0.1 to 10% by weight. The fibers to be treated are, for example, natural fibers such as cotton and silk,
Semi-synthetic fibers such as acetate, polyester, nylon,
Examples thereof include synthetic fibers such as polyamide and polyacrylate, and blended and knitted fabrics thereof.

When the amino-modified silicone of the present invention is used as a hair treatment agent, for example, a hair shampoo, a hair rinse, a hair conditioner, a hair treatment, a hair lotion, a hair liquid, a hair tonic, etc., it is used after emulsified or dispersed in water. Is preferred. Other components, for example, nonionic surfactants such as alcohol ethers, esters and amides, fatty acid soaps, alkyl benzene sulfonic acids, alkyl ether sulfates, alkyl sulfates and anionic surfactants such as alkyl sulfonic acids Agents, cationic surfactants such as ammonium-based, amphoteric surfactants such as carbobetaine-based and sulfobetaine-based, silicon-based surfactants such as polysiloxane, foaming agents, hydrotropes,
It may contain sequestering agents, alkalis such as sodium hydroxide, solvents, fragrances, dyes and the like. The amount used when used as a hair treatment agent is not particularly limited, but is preferably 0.01 to 50% by weight relative to the total amount, and 0.05 to 50% by weight.
40% by weight is more preferable, and 0.1 to 30% by weight is further preferable.

When used as a resin additive, effects such as improvement of blocking resistance of the used resin can be exhibited. Examples of resins to be used include olefin resins, acrylic resins, styrene resins, vinyl acetate resins, polyester resins, polyamide resins, polyimide resins, polyaryl ether resins, epoxy resins, urethane resins, and halogenated olefins. And the like. The amount used is not particularly limited, but is 0.0
01 to 30% by weight is preferable, and 0.005 to 20% by weight.
Is more preferable, and 0.01 to 10% by weight is further preferable.

[0022]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following examples, parts and percentages are by weight unless otherwise specified. <Modifier of the Present Invention> Modifier 1: Dimethyldiallylammonium chloride

Embedded image

Modifier 2:

Embedded image

Modifier 3:

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Modifier 4:

Embedded image

<Compound having a reactive carbon-carbon double bond in the molecule>

Embedded image CH ₂ ＣＨCHCH ₂ O (CH ₂ CH ₂ O) ₁₀ H

<Compound having Si—H bond in molecule> Compound having Si—H bond in molecule 1:

Embedded image

Compound 2 having a Si—H bond in the molecule:

Embedded image (In the formula, / represents random polymerization)

Compound 3 having a Si—H bond in the molecule:

Embedded image (In the formula, / represents random polymerization)

Compound having a Si—H bond in the molecule 4:

Embedded image (In the formula, / represents random polymerization)

(Example 1) In a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirrer, 63 parts of a 60% aqueous solution of the above-mentioned denaturing agent 1, 100 parts of isopropyl alcohol, 0.1 part One part of a 1% solution of isopropyl alcohol chloroplatinate was added. Heat the system to 80 ° C,
1: 185 parts of the compound having a Si—H bond in the molecule was dropped over 30 minutes, and after completion of the dropping, the temperature was raised to 90 ° C. and further heated for 1 hour. Thereafter, the solvent was removed under reduced pressure to obtain the amino-modified silicone 1 of the present invention.

The amino-modified silicones 2 to 6 of the present invention were obtained in the same manner as shown in the following table. The numbers in the table represent parts.

[Table 1]

The following silicone compounds 1 to 3 were used as comparative silicone compounds. Comparative Silicone 1: Polydimethylsiloxane

Comparative Silicone 2:

Embedded image (In the formula, / represents random polymerization)

Comparative Silicone 3:

Embedded image (In the formula, / represents random polymerization)

(Test 1: Skin irritation test) Healthy adult 2
The amino-modified silicone 1 of the present invention was prepared using 5 subjects as subjects.
7 and Comparative Silicone 1-3 are attached to the upper arm and
The state of the skin after 8 hours was visually observed and evaluated according to the following criteria. ：: 0 people showed slight inflammation △: 1 to 3 people showed even slight inflammation ×: 4 or more people showed even slight inflammation The results are as follows.

[0037]

[Table 2]

(Test 2: Fiber Flexibility Test) A cotton broad having a length of 30 cm and a width of 20 cm was dissolved in an isopropyl alcohol solution in which each of the amino-modified silicones 1 to 7 of the present invention and the comparative silicones 1 to 3 were dissolved in 0.3%. The cloth No. 60 was dipped, dried and then heated at 120 ° C. for 3 minutes. The treated fabric was evaluated according to the following criteria. After the completion of the heat treatment, the test cloth was washed under the following conditions, and the same evaluation was performed.

<Conditions of washing> Washing machine: Targotometer (120 rpm) Temperature: 30 ° C. Hardness: 50 ppm (artificial hard water) Bath ratio: 1:30 Under the above conditions, the test cloth was subjected to the following steps as one step.
Washed 0 times. Washing (10 minutes) │ Dehydration (squeezing rate 120%) │ Rinse (3 minutes)) │) Repeat twice Dehydration (squeezing rate 120%)) │ Drying (60 minutes, put test cloth in washing net, dry clothes Machine)

[0040]

[0041]

[Table 3]

(Test 3: Antibacterial Test) The test cloth used in Test 2 was cut into a length of 3 cm and a width of 3 cm, sterilized at 105 ° C. for 2 hours, poured into a bouillon suspension of the test bacteria, and sealed. The number of bacterial cells produced after 18 hours at 37 ° C. in the medium was measured, and the increase or decrease in the number of bacterial cells was determined.

[0043]

[Table 4] 1) Viable cell count before test 3.0 × 10 ⁵ 2) Viable cell count before test 4.2 × 10 ⁵

(Test 4: Hair treatment test) The amino-modified silicones 1 to 7 of the present invention and the comparative silicones 1 to 3 were
It was compounded according to the following formulation. (Shampoo) Polyoxyethylene (5) sodium lauryl ether sulfate 15% Coconut oil fatty acid diethanolamide 3% Amino-modified silicone 1 to 6 of the present invention or comparative silicone 1 to 3 1.5% Fragrance 0.2% Purified water balance 100% in total

(Rinse) Stearyl trimethylammonium chloride 1.5% Cetanol 2% Amino-modified silicone 1-6 of the present invention or comparative silicone 1-3 0.2% Fragrance 0.2% Purified water balance Total 100%

(Hair oil) Octamethylcyclotetrasiloxane 40% Amino-modified silicone of the present invention 1 to 6 or comparative silicone 1 to 38%

The above three types of hair treatment agents were tested by panelists. Foaming, conditioning property and tackiness were evaluated according to the following criteria. ○: clearly superior to general-purpose products △: roughly equivalent to general-purpose products ×: clearly inferior to general-purpose products

[0048]

[Table 5]

(Test 5) 50 parts of styrene, 50 parts of butyl acrylate, 2 parts of acrylic acid, and ethyl acetate 1 as a solvent
Solution polymerization of 00 parts with benzoyl peroxide as a catalyst,
Amino-modified silicones 1 to 7 of the present invention and comparative silicones 1 to 3 were added to the obtained copolymer solution at a solid content of 1%, and applied to a polyethylene film to prepare a coating film. ASTM; D1893-67 for this coating
The blocking resistance of the coating film was measured according to.

[0050]

[Table 6]

[0051]

The effect of the present invention is to provide a modifier for a compound having a Si—H bond in the molecule. Another effect of the present invention is to provide a novel amino-modified silicone and a specific use of the compound. According to the modifier of the present invention, a compound having a Si—H bond in a molecule can be modified.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 15/643 D06M 15/643

Claims (8)

[Claims] 1. The following general formula (1): (Wherein, R and R ′ represent a hydrogen atom or a methyl group, R ¹ and R ² represent a hydrocarbon group or a hydrocarbon group containing an oxygen atom, and X represents an anionic atom or an anionic group. A modifier for a compound having a Si-H bond in the molecule, comprising the compound represented by the following formula: 2. A compound having a Si—H bond in a molecule is represented by the following general formula (2): (Wherein, R ³ is independently the same or different hydrogen atom,
It represents a hydroxyl group, a hydrocarbon group or a hydrocarbon group having an oxygen atom and / or a silicon atom, n represents 0 or a number of 1 or more, and at least one of 2n + 6 R ³ represents a hydrogen atom. The modifying agent according to claim 1, which is a compound represented by the formula: 3. A modifier comprising a compound represented by the general formula (1) and a compound represented by the formula (2)
An amino-modified silicone obtained by reacting a compound having an H bond. 4. A modifier comprising a compound represented by the general formula (1), a compound having a reactive carbon-carbon double bond in the molecule, and a Si-containing compound represented by the general formula (2) in the molecule.
An amino-modified silicone obtained by reacting a compound having an H bond. 5. A surfactant comprising the amino-modified silicone according to claim 3 as an essential component. 6. A fiber treating agent comprising the amino-modified silicone according to claim 3 as an essential component. 7. A hair treatment agent comprising the amino-modified silicone according to claim 3 as an essential component. 8. A resin additive comprising the amino-modified silicone according to claim 3 as an essential component.